Green chemistry aims to mitigate the environmental, health, and economic concerns associated with traditional chemical processes by increasing reaction efficiencies, reducing waste, using innocuous materials, and developing biodegradable products. Poly(anhydride-esters) (PAEs) are biodegradable surface-eroding polymers that represent such biodegradable products, exhibiting a controlled, near zero-order release of naturally occurring bioactives. Current synthesis of bioactive-based PAEs use excessive solvents, hazardous purification chemicals, and multistep reactions. Therefore, improved and/or less-toxic methodologies for preparing PAEs are needed, as well as intermediates that are useful in the preparation of such polymers.